Process for hydroprocessing of non-petroleum feedstocks

ABSTRACT

A method of hydroprocessing is performed wherein non-petroleum feedstocks, such as those containing from about 10% or more olefinic compounds or heteroatom contaminants by weight, are treated in a first reaction zone to provide reaction products. The process involves introducing the feedstock along with diluents or a recycle and hydrogen in a first reaction zone and allowing the feed and hydrogen to react in a liquid phase within the first reaction zone to produce reaction products. The reaction products are cooled and/or water is removed from the reaction products. At least a portion of the cooled and/or separated reaction product are introduced as a feed along with hydrogen into a second reaction zone containing a hydroprocessing catalyst. The feed and hydrogen are allowed to react in a liquid phase within the second reaction zone to produce a second-reaction-zone reaction product.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.13/353,856, filed Jan. 19, 2012, now U.S. Pat. No. 9,096,804, issuedAug. 4, 2015, which claims the benefit of U.S. Provisional ApplicationNo. 61/434,414, filed Jan. 19, 2011, each of which is incorporatedherein by reference in its entirety for all purposes.

BACKGROUND

In conventional hydroprocessing of petroleum products it is necessary totransfer hydrogen from a vapor phase into the liquid phase where it willbe available to react with a petroleum molecule at the surface of thecatalyst. This is accomplished by circulating very large volumes ofhydrogen gas and the petroleum oil through a catalyst bed. The petroleumoil feed and the hydrogen flow through the catalyst bed and the hydrogenis absorbed into a thin film of oil that is distributed over thecatalyst. Because the amount of hydrogen required can be large, e.g.1000 to 5000 SCF/bbl of liquid, the reactors are very large and canoperate at severe conditions, from a few hundred psi to as much as 5000psi, and temperatures from around 250° F.-900° F.

The temperature inside the reactor is difficult to control inconventional systems. While the temperature of the oil and hydrogen feedintroduced into the reaction zone can be controlled, once thefeed/hydrogen mixture is inside the reaction zone no adjustments to thesystem can be made to raise or lower the temperature of the oil/hydrogenmixture. Any changes in the reaction zone temperature must beaccomplished through an outside source. As a result, conventionalsystems often inject cold hydrogen gas into the reaction zone if itbecomes too hot. This method of cooling a reactor is expensive and is apotential safety risk.

While controlling the temperature of the reaction zone is often adifficult task in conventional systems, controlling the pressure of thehydroprocessing system is a much easier task. Pressure control systemsare used to monitor the pressure of the system. The controls are used torelease pressure through a valve or valves if the pressure becomes toogreat, and to increase the pressure of the system if the pressurebecomes too low. A pressure control system cannot be used to control thepressure on a single hydroprocessing reactor, however. This is of noserious consequence, however, because pressure may be maintained on theentire system, but not on individual reactors.

One of the biggest problems with hydroprocessing is catalyst coking.Coking occurs when hydrocarbon molecules become too hot in anenvironment where the amount of hydrogen available for reaction isinsufficient. The hydrocarbon molecules within the reactor crack to thepoint where coke, a carbonaceous residue, is formed. Cracking can takeplace on the surface of the catalyst, leading to coke formation anddeactivation of the catalyst.

High-contaminant and/or high-olefinic feedstocks further complicate thehydroprocessing process. High-contaminant and/or high-olefinicfeedstocks may include petroleum materials but primarily includenon-petroleum products, such as renewable feedstocks derived frombiological sources. These may be based on vegetable- or animal-derivedmaterials, such as vegetable and animal oils. Such high-contaminantand/or high-olefinic feedstocks may also include pyrolysis oils derivedfrom biomass materials, such as cellulosic biomass materials, or coal.These non-petroleum feedstocks may be highly olefinic and/or containhigh levels of heteroatom contaminants, such as oxygen, nitrogen,sulfur, etc. Such olefinic compounds and heteroatom contaminants may beat levels of from about 10% by weight or more of the feed.

In order to produce a valuable product from such highly olefinic andhighly contaminated feedstocks, a large amount of hydrogen is required,roughly 1500-4000 scf/bbl. Furthermore, these reactions are highlyexothermic. They generate a great deal of heat, significantly more thanwhat is found in a typical hydroprocessing process of petroleumproducts. The excessive amounts of heat generated put the entire processat great risk. One concern is the effect of such large quantities ofheat on the catalyst. It is widely known that overheating, andsubsequent coking, is one of the most common causes of catalystdeactivation. In a process that generates significantly more heat thanthe typical hydroprocessing process, temperature control in order tomaintain catalyst activity is crucial. The most serious threat involvedin the hydroprocessing of high-contaminant and/or high-olefinicfeedstocks, however, is the risk of creating a runaway reaction, areaction that generates so much heat that the process can no longer bebrought under control. Despite turning off heaters and maximizing allcooling efforts, a runaway reaction can continue to heat and has thepotential to cause serious damage to the reactor and process equipment.Runaway reactions contribute to a significant number of refineryexplosions, damaging equipment, slowing or stopping production, andendangering workers. Consequently, the heat generated by thehydroprocessing of high-contaminant and/or high-olefinic feedstocks isone the greatest problems that must be surmounted.

An additional concern that is unique for high-contaminant feedstocks isthe effect of hydroprocessing byproducts on the system. Water, hydrogensulfide, ammonia, sulfur, carbon, and nitrogen oxides are all commonbyproducts created during hydroprocessing reactions. While thesebyproducts are undesirable in the finished product and must eventuallybe removed from the finished product, when using conventional petroleumfeedstocks, these byproducts are not generally present in amountssignificant enough to pose any real threat to the integrity of theprocess. This is not true for high-contaminant feedstocks. Thehydroprocessing of these feedstocks results in much larger quantities ofthese byproducts being present in the system. These byproducts,particularly water, can be especially harmful to the catalyst. If wateris allowed to build up in the catalyst bed, a separate aqueous phase canform. This aqueous phase is extremely harmful to the catalyst,essentially causing it to dissolve inside the reactor. In addition,hydrogen sulfide and ammonia, in large quantities, are widely known toinhibit catalyst activity. Therefore, it is of great importance that thequantities of these byproducts created during the hydroprocessing ofhigh-contaminant feedstocks be controlled to prevent or minimize anydamage they may cause to the system.

Because prior art methods do not adequately address the problemsassociated with hydroprocessing highly contaminated and/or highlyolefinic feedstocks, improvements are needed.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the present invention, and theadvantages thereof, reference is now made to the following descriptionstaken in conjunction with the accompanying figures, in which:

FIG. 1 is a process flow diagram schematic showing a hydroprocessingsystem that may be used for hydroprocessing high-contaminant and/orhigh-olefinic feedstocks;

FIG. 2 is a process flow diagram schematic showing a hydroprocessingsystem that may be used for hydroprocessing of high-contaminant and/orhigh-olefinic feedstocks and that employs reactors having multiplereaction zones;

FIG. 3 is a process flow diagram schematic showing a hydroprocessingsystem employing flash vessels to facilitate separation of reactionproducts; and

FIG. 4 is a schematic representation of a reactor that may be used inthe hydroprocessing system for hydroprocessing high-contaminant and/orhigh-olefinic feedstocks.

DETAILED DESCRIPTION

In accordance with the present invention, a process has been developedwherein high-contaminant feedstocks or feedstocks with high-olefiniccontent can be treated. As used herein, high-contaminant feed stocks arethose containing heteroatoms, such as sulfur, nitrogen, oxygen, andmetals, which may be at levels of from 10% or more by weight of thefeed. High-olefinic feedstocks are those having from 10% or more ofolefinic molecules by weight of the feed. Such feedstocks can beconverted, through hydroprocessing, into useful products while keepingreaction zone temperatures well-controlled and maintaining catalystactivity. As used herein, the term “hydroprocessing” is meant to includehydrotreating, hydrofinishing, hydrorefining, hydrocracking,hydroisomerization, and hydrodemetalization.

Such high-contaminant and/or high-olefinic feedstocks may includenon-petroleum products, such as renewable feedstocks derived frombiological sources. These may be derived from or based on vegetable,animal, and cellulosic materials, and combinations of such materials.Such high-contaminant and/or high-olefinic feedstocks may includevegetable oils, animal oils, and other bio oils. The high-contaminantand/or high-olefinic feedstocks may also include pyrolysis oils frombiomass materials, such as cellulosic biomass materials, or coal. Thesefeedstocks may be highly olefinic and/or contain heteroatoms, such asoxygen, nitrogen, sulfur, metals, etc. As used herein, with respect toolefinic compounds weight percentages are based on weight of theolefinic molecules. With respect to heteroatom contaminants, weightpercentages are based upon the weight of the heteroatoms. Such olefiniccompounds and heteroatom contaminants may be at levels of from about10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% or more by weight or more ofthe feedstock. In particular, the olefinic compounds and heteroatomcontaminants may make up from about 10% to about 50% by weight of thefeedstock. In certain embodiments, the feed stock may have an oxygencontent of from about 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% byweight or more.

It should be understood that with respect to any concentration or amountrange listed or described herein as being useful, suitable, or the like,it is intended to include every concentration or amount within therange, including the end points, and is to be considered as having beenspecifically stated. For example, “a range of from 1 to 10” is to beread as indicating each and every possible number along the continuumbetween about 1 and about 10. Thus, even if specific data points withinthe range, or even no data points within the range, are explicitlyidentified or refer to only a specific few, it is to be understood thatthe inventors appreciate and understand that any and all data pointswithin the range are to be considered to have been specified, and thatthe inventors are in possession of the entire range and all pointswithin the range.

The high-contaminant and/or high-olefinic feedstock may be entirely anon-petroleum product or material and be treated in accordance with theinvention without the addition or combining with any petroleumfeedstocks that are treated. In most instances, the high-contaminantand/or high-olefinic feedstock is a renewable material that is derivedfrom biological sources and may also include pyrolysis oils from biomassmaterials, such as cellulosic biomass materials, or coal. While coal isnot generally considered a renewable material, it is a non-petroleummaterial and for purposes of the present discussion is meant to beincluded with renewable and biomass materials because of its similarproperties and should be construed as such unless otherwise stated or isapparent from its context.

The high-contaminant and/or high-olefinic feedstock may be introducedinto a reactor along with hydrogen gas under conditions so thatsubstantially all the feed and hydrogen introduced may be in acontinuous liquid phase as a hydrogen-gas-free liquid feed stream priorto introduction into the reactor. This may be accomplished by the use ofa diluent that is combined with the feed and hydrogen, as well assetting of the reactor conditions so that all of the hydrogen requiredin the hydroprocessing reactions is available in solution. The use ofsuch methods wherein in a liquid diluent is used to dissolve hydrogengas so that it is present in solution for reaction is described in U.S.Pat. Nos. 6,123,835; 6,428,686; 6,881,326; 7,291,257; and 7,569,136,each of which is incorporated herein by reference for all purposes.

The feedstock and hydrogen can then be fed as a liquid to a reactor,such as a plug flow or tubular reactor, packed with hydroprocessingcatalyst where the oil and hydrogen react. The reactor may contain nohydrogen gas. In other cases there may be small amounts of hydrogen gasthat may be present in the reactor that evolve from solution or that mayotherwise be present or introduced into the reactor. In such cases, thereactor may contain from about 10%, 5%, 4%, 3%, 2%, 1% or less of anyhydrogen gas by total volume of the reactor. This hydrogen gas withinthe reactor may eventually enter into solution as the hydrogen insolution is consumed during the reaction. Such hydrogen gas, as well asany other gases (e.g. light end hydrocarbons), may also be vented fromthe reactor, if desired. In certain embodiments, no hydrogen gas may beadded directly to the reactor, with all hydrogen for reaction beingmixed with the feed and any diluent prior to introduction into thereactor. In many cases, no additional hydrogen is required to be added,therefore, hydrogen recirculation is avoided, as in trickle bedreactors. The large trickle bed reactors used in conventionalhydroprocessing systems can therefore be replaced by much smallerreactors. Elimination of the recycle compressor and the use of, forexample plug flow or tubular reactors, may greatly reduce the capitalcost of the hydrotreating process. The continuous liquid phase reactorsalso provide more control over the reaction zone temperature, acting asa heat sink to stabilize the temperature inside the reaction zone. Theadded diluent also serves to increase the quantity of hydrogen capableof being dissolved into the feedstock and also serves to aid inmaintaining a single liquid phase inside the reaction zone.

In other embodiments, the high-contaminant and/or high-olefinicfeedstock may be introduced as a liquid phase that contains a quantityof hydrogen gas contained in the liquid, with or without any additionaldiluents. Such quantities of hydrogen gas in the liquid feed may besmall, such as from about 1% to about 15% by volume of the feed. Thehydrogen gas may be entrained in the liquid feed without separation ofthe hydrogen gas prior to being introduced into the reactor. Such excesshydrogen gas may be used as make up as hydrogen is consumed during thereaction. Furthermore, such hydrogen gas may remain in the reactorwithout venting of excess hydrogen gas from the reactor. If venting ofhydrogen gas does occur, it may be vented without facilitating thecontrol of any liquid level within the reactor.

In certain embodiments, hydrogen gas may be present in the reactor inamounts of from greater than 10% to about 60% of hydrogen gas by volumeof the reactor, more particularly from greater than 10%, 15%, 20%, 25%,30%, 35%, 40%, 45%, 50%, or 55% to about 60% by volume of the reactor.Such hydrogen gas within the reactor may be that that is added directlywith the feed, without adding hydrogen gas directly into the reactor.Hydrogen gas may be added directly to the reactor in some embodiments,however.

The reactors for hydroprocessing as described herein contain ahydroprocessing catalyst. Such hydroprocessing catalysts are well knownin the art. The amount of catalyst used in the reactors may be that thatprovides sufficient conversion. The amount of catalyst may provide aLHSV of from about 0.1 to about 10 hr⁻¹. Reactor temperatures typicallyrange from about 100 to about 500° C.

In the case of a feedstock with high oxygen content, as in, for example,a renewable feedstock such as animal or vegetable oil, etc., the oxygen,under hydroprocessing conditions inside the reaction zone, is convertedinto water. The greater the quantity of water produced, the more likelyit is that two distinct liquid phases will form inside the reactionzone: a hydrocarbon phase and an aqueous phase. If an aqueous liquidphase forms inside the reaction zone, severe damage to the catalyst mayresult. To maintain catalyst activity, the water created during thereaction between hydrogen and oxygen must be held in solution with thehydrocarbon component and dissolved hydrogen. A diluent or recyclestream added to the feed may provide a greater capacity for holdinghydrogen in solution. The diluent or recycle also facilitates adjustingthe capacity for holding water in solution, without creating an aqueousphase. In many cases diluent is provided by a product stream of thehydroprocessing reaction that is recycled and added as a diluent. Inother cases, such as during startup, diluent may be added from anexisting or previously provided diluent source. As used herein, the term“diluent” may therefore be construed as diluent provided as a separatesource or as a recycle stream from the process, unless expressly statedotherwise or is apparent from its context. With more diluent or recycle,higher amounts of water, as well as other byproducts, may be held insolution. The diluent or recycle may also serve to stabilize reactionzone temperatures and increases the capacity of the liquids inside thereaction zone for holding heat, dissolved hydrogen, and reactionby-products.

Though the diluent is effective in controlling reaction zonetemperatures and mitigating the effects of reaction by-products inhydroprocessing systems utilizing traditional feedstocks, the enormousquantities of heat and reaction by-products produced by a systeminvolved in the hydroprocessing of high-contaminant and/or high-olefinicfeedstocks may not be managed solely through the addition of a diluentor recycle. To overcome such shortcomings, multiple reactors, ormultiple reaction zones, may be used. This allows for the removal ofheat and reaction by-products, if necessary or desired, in betweenreactors and/or reaction zones. Heat can be removed from the effluentbetween reaction zones by cooling the reaction zone effluent. Reactionby-products can be removed by forming a liquid phase and a gas phasefrom the cooled reaction products, and removing the gas phase ahead ofthe next reaction zone. Alternately, the reaction zone effluent can beflashed without any previous cooling step, removing a portion of thereaction by-products and dissipating a great deal of heat with theflash. The removal of additional heat and reaction by-products betweenreaction zones, in combination with the benefits inside the reactor(s)of operating in a liquid phase and using a liquid diluent or liquidrecycle, creates a process that can be safely and efficiently managehighly exothermic reactions and large amounts of catalyst-deactivatingreaction by-products, such as those from high-contaminant and/orhigh-olefinic feeds, without reducing conversion rates.

The process wherein high-contaminant and/or high-olefinic feedstocks areconverted through hydroprocessing into useful products keeps reactionzone temperatures well-controlled and maintains catalyst activity. Thisis accomplished by utilizing the methods described herein to stabilizethe temperature of liquids inside the reaction zone, to dissipate heatfrom reaction zone effluents prior to entering subsequent reactionzones, to minimize the effects of reaction by-products on catalyst bedsinside reaction zones, and to remove harmful reaction by-productsbetween reaction zones. The temperature of the liquids inside thereaction zone is stabilized, at least in part, by creating a liquidphase solution inside the reaction zone. This is accomplished by mixingand/or flashing the hydrogen and the feed to be treated in the presenceof a diluent having a relatively high solubility for hydrogen. Excesshydrogen may be mixed and/or flashed into the hydrocarbon feed to betreated and diluent solution so that the maximum capacity of the feedand diluent solution for hydrogen is utilized, with or without anyamounts of hydrogen gas entrained in such liquid.

The type and amount of diluent added, as well as the reaction zoneconditions, can be set so that all of the hydrogen required in thehydroprocessing reaction is available in solution. The feed to betreated, diluent, and hydrogen solution can then be fed to a plug flow,tubular or other reactor packed with catalyst where the feed andhydrogen react.

The reactors may be altered in configuration and in number toaccommodate the specifications required of the product, given a specificfeed. To achieve the desired product specifications from a particularlycontaminated feed may necessitate the addition of one or more additionalreactors and/or reaction zones. Even in the case where multiplereactors, or reaction zones, are required, the reactors of the presentinvention are preferred to conventional reactors because their smallersize and more simple design may result in a reduction of capital costwhen compared to conventional systems. In addition to utilizing multiplereactors, it may also be possible to house multiple catalyst beds andreaction zones within a single reactor housing. The creation ofmultiple-bed reactors further lowers capital cost by utilizing a singlereactor vessel to house multiple catalyst beds. The catalyst beds maycontain the same catalyst type, or they may contain different catalysttypes to more efficiently accomplish the product specification goal.

Most of the reactions that take place in hydroprocessing are highlyexothermic, and as a result, a great deal of heat is generated in thereaction zone. The temperature of the reaction zone can be controlled byusing a recycle stream. A controlled volume of reaction zone effluentcan be recycled back to the front of the reaction zone, using a reheateras necessary, and blended with fresh feed and hydrogen. The recyclestream absorbs heat created by the reaction of the feed and hydrogen onthe catalyst and reduces the temperature rise through the reaction zone.The reaction zone temperature can be controlled by controlling the freshfeed temperature, using a preheater as necessary, and the amount ofrecycle. In addition, because the recycle stream contains molecules thathave already reacted, it also serves as an inert diluent, as previouslydiscussed.

The use of a liquid phase reaction zone provides an additional level ofcontrol of the temperature inside the reaction zone. The advantage of aliquid phase reactor is that liquids, in general, have higher heatcapacities than gases. The greater the heat capacity of a givenmaterial, the greater ability that material has for absorbing heat fromits surroundings while undergoing a minimal increase in temperatureitself. A liquid phase reactor acts as a heat sink, absorbing excessheat from the reaction zone to equalize the temperature throughout. Withthe introduction of the liquid phase reactor using typicalhydroprocessing feedstocks, the process becomes much closer to beingisothermal, reducing a typical 40° F. to 60° F. temperature differencebetween the reactor inlet and reactor outlet to approximately a 5° F. to15° F. temperature difference. In addition to reducing the temperaturedifference between the reactor inlet and reactor outlet temperatures,the liquid phase reactor also serves to greatly reduce the problem ofhot spots developing within the catalyst bed. Consequently, with the useof liquid phase hydroprocessing according to the present invention,coking can be nearly eliminated or minimized because there is alwaysenough hydrogen available in solution to avoid coking when crackingreactions take place. This can lead to much longer catalyst life andreduced operating and maintenance costs.

While conventional hydroprocessing of typical hydrocarbon feedstocks maygenerate heat, the amount of heat generated in these reactions isinsignificant compared to the heat generated during the hydroprocessingof highly contaminated and/or highly olefinic feedstocks, as describedherein. These feedstocks, whether a hydrocarbon feedstock or abiological or renewable feedstock, require massive amounts of hydrogen.Consequently, hydroprocessing of these materials creates significantlymore heat than can be managed using a conventional hydroprocessingprocess. To create quality products from these high-contaminant and/orhigh-olefinic feedstocks and to maintain catalyst activity andintegrity, more must be done to remove heat and control the temperatureof the process.

The extreme quantities of heat can be managed by keeping reaction zonessmall and utilizing multiple reaction zones to accomplish the goal, byproviding an adequate quantity of liquid diluent or recycle to increasethe heat capacity of the liquids inside the reaction zone(s), and byproviding a method of removing heat from the liquid reactants betweenreaction zones using heat exchangers or flash vessels to lower thetemperature of the liquid reactants prior to entry into subsequentreaction zones.

Another problem found in hydroprocessing is the production of reactionby-products, namely light end hydrocarbon gases. These molecules,predominately methane, are an undesirable product which, in great enoughquantities, must be recovered, at additional cost. These light endsincrease in quantity as the temperature of the reaction goes up. Theproblem of light end production is further compounded by the tendencyfor a reactor to develop hot spots, areas where the temperatureincreases significantly above the set temperature for the reactor. Tocombat this occurrence, conventional hydroprocessing systems employ theuse of quench boxes which are placed throughout the reactor. The quenchboxes serve to inject cold hydrogen into the reactor to reduce thetemperature inside the reactor. Not only is hydrogen an expensive choicefor cooling the reactor, it can pose a safety hazard. The design of thequench boxes and the method of controlling how they introduce hydrogeninto the reactor are vital, because an error could cause the loss ofcontrol of the entire system. A runaway reaction could be started,possibly creating an explosion.

Using liquid phase hydroprocessing, cracking is greatly reduced, oftenby a 10-fold reduction, through the use of a liquid phase reactorworking also as a heat sink to create a reactor environment that isclose to isothermal. The amounts of light end hydrocarbons are thereforesignificantly reduced. This near isothermal environment eliminates theneed for cold hydrogen quench boxes, reduces the capital cost ofhydrogen required for the process and increases the safety of thesystem.

In the hydroprocessing of high-contaminant and/or high-olefinicfeedstocks, especially those of biological origin, the reactionby-products produced during hydroprocessing are a serious concern.Higher feedstock contaminant levels translate to greater quantities ofreaction by-products from those contaminants: hydrogen sulfide, ammonia,sulfur, carbon, and, of perhaps greatest concern, water. In large enoughquantities, these by-products can wreck havoc on catalyst beds. Indeed,depending on the oxygen content of the feed, water produced as areaction product in the reactor or reactors may make up from at least10%, 20%, 30%, 40%, 50% or more by weight of the reaction productsproduced in such reactor or reactors. Water, specifically, has thepotential to come out of solution with the hydrocarbonaceous reactantsand products. If this occurs, wherein two separate liquid phases, i.e.an aqueous phase and a hydrocarbonacous phase, are present in thereaction zone, the aqueous phase will rapidly deactivate the catalystand may effectively dissolve it inside the reactor.

The buildup of hydrogen sulfide and ammonia are also of great concern,as they are both widely known to inhibit catalyst activity. With thehydroprocessing of high-contaminant and/or high-olefinic feedstocks, theproduction of these undesirable reaction by-products may occur at levelsto cause concern. In order to create quality products from thesehigh-contaminant and/or high-olefinic feedstocks and maintain catalystactivity and integrity, the quantities of these reaction by-products insolution must be controlled so as to prevent their build-up to levelsthat will compromise the process.

The combination of controlling reaction zone temperature and managingthe quantity of harmful reaction by-products in the process: utilizingmultiple small reaction zones, providing an adequate quantity of adiluent or recycle to increase the capacity of the liquids inside thereaction zone for holding heat and keeping reaction by-products insolution, and the use of heat exchangers, separators, and/or flashvessels to remove undesirable quantities of heat and reactionby-products from the liquid reactants prior to entry into subsequentreaction zones, all facilitate making the hydroprocessing of highlycontaminated and/or highly olefinic feedstocks a viable option.

Referring to FIG. 1, a flow diagram schematic of a hydroprocessingsystem 100 that is configured in accordance with the invention is shown.A high-contaminant and/or high-olefinic feedstock 101, which may be arenewable material, such as pyrolysis oil or those non-petroleummaterials previously described, is passed through preheater 102.Preheater 102 may only be required during unit startup. After theinitial startup period, the feedstock 101 is preheated as it passesthrough a series of heat exchangers: 115, 135, 155, 175, and 195, andpreheater 102 is no longer necessary. The heated high-contaminant and/orhigh-olefinic feedstock 101 is then blended with a diluent 103 to form aliquid feedstock-diluent mixture 104. The amount of diluent 103 addedmay be that sufficient to dissolve a preselected amount of hydrogen inthe combined feed-diluent mixture; to maintain the temperature withinthe reactor(s) below a preselected temperature; or to adjust thecapacity of the liquid phase to dissolve or carry water; or acombination of these.

A controlled amount of hydrogen gas 105 is mixed with and dissolved intofeedstock-diluent mixture 104 to form a liquid phase feed, diluent, andhydrogen mixture 109.

The liquid feedstock, diluent, and hydrogen mixture 109 is then fed intoreactor 110 and reacted in the reactor's reaction zone(s) to form aliquid phase reacted effluent 112 containing reaction products. Anyevolved or excess undissolved hydrogen gas and light ends may be ventedfrom the top of the reaction zone(s) through vent 113 to facilitatecontrolling the quantity of liquids in the reactor. In otherembodiments, hydrogen gas remains in the reactor(s) with no venting ofhydrogen gas from the reactor(s). Alternatively, any venting of hydrogengas from the reactor may be for purposes other than for controlling thequantity of liquid within the reactor, with the liquid level withinreactor 110 being controlled by the input of hydrogen at 105.

The reacted effluent 112 is then passed through heat exchanger 115 tolower the temperature of the reacted effluent 112 and to facilitate theseparation of light end hydrocarbons, water, other reaction by-products,and excess hydrogen from the reacted effluent 112 into the gas phase tocreate multi-phase reacted effluent 117 comprising: 1) a gas phasereacted effluent and a liquid phase hydrocarbonaceous reacted effluentor 2) a gas phase reacted effluent, a liquid phase hydrocarbonaceousreacted effluent, and liquid water or aqueous phase. The multi-phasereacted effluent 117 is then introduced into separator 120 and separatedinto as many as three separate components: liquid water 122,hydrocarbonaceous reacted effluent 124, and gas phase reacted effluent126 comprising light ends and excess hydrogen gas. The rate at which thegas phase reacted effluent 126 exits the separator 120 is controlled byvalve 127. Note that, depending on the feedstock and process conditions,liquid water 122 may not be formed in the separator. If water is createdas a reaction by-product in reactor 110, it may, alternately, remaindissolved in the hydrocarbonaceous phase of the reacted effluent 117 orit may also move into the gas phase as a vapor and exit the separator120 with the gas phase reacted effluent 126.

Additional hydrogen gas 128 is then mixed with and dissolved into liquidhydrocarbonaceous reacted effluent 124 and fed into intermediate reactor130 and reacted in the reactor's reaction zone(s) to form a liquid phasereacted effluent 132. Any excess undissolved hydrogen gas and light endsmay be vented from the top of the reaction zone(s) through vent 133. Thequantity of hydrogen gas 128 added to the hydrocarbonaceous reactedeffluent 124 is adjusted by valve 129, which is controlled by levelcontroller 131. The reacted effluent 132 is then passed through heatexchanger 135 to lower the temperature of the reacted effluent and tofacilitate the separation of light end hydrocarbons, water, otherreaction by-products, and excess hydrogen from the reacted effluent 132into the gas phase to create multi-phase reacted effluent 137comprising: 1) a gas phase reacted effluent and a liquid phasehydrocarbonaceous reacted effluent or 2) a gas phase reacted effluent, aliquid phase hydrocarbonaceous reacted effluent, and liquid water oraqueous phase. The multi-phase reacted effluent 137 is then introducedinto separator 140 and separated into as many as three separatecomponents: liquid water or aqueous phase 142, liquid hydrocarbonaceousreacted effluent 144, and gas phase reacted effluent 146. The rate atwhich the gas phase reacted effluent 146 exits the separator 140 isadjusted by valve 147.

Additional hydrogen gas 148 is then mixed with and dissolved into theliquid hydrocarbonaceous reacted effluent 144 and fed into intermediatereactor 150 and reacted in the reactor's reaction zone(s) to form aliquid phase reacted effluent 152. Excess undissolved hydrogen gas andlight ends may be vented from the top of the reaction zone(s) throughvent 153. The quantity of hydrogen gas 148 added to thehydrocarbonaceous reacted effluent 144 is adjusted by valve 149, whichis controlled by level controller 151. The reacted effluent 152 is thenpassed through heat exchanger 155 to lower the temperature of thereacted effluent and to facilitate the separation of light endhydrocarbons, water, other reaction by-products, and excess hydrogenfrom the reacted effluent 152 into the gas phase to create multi-phasereacted effluent 157 comprising: 1) a gas phase reacted effluent and aliquid phase hydrocarbonaceous reacted effluent or 2) a gas phasereacted effluent, a liquid phase hydrocarbonaceous reacted effluent, andliquid water or aqueous phase. The multi-phase reacted effluent 157 isthen introduced into separator 160 and separated into as many as threeseparate components: liquid water or aqueous phase 162, liquidhydrocarbonaceous reacted effluent 164, and gas phase reacted effluent166. The rate at which the gas phase reacted effluent 166 exits theseparator 160 is adjusted by valve 167.

Additional hydrogen gas 168 is then mixed with and dissolved into theliquid hydrocarbonaceous reacted effluent 164 and fed into intermediatereactor 170 and reacted in the reactor's reaction zone(s) to form aliquid phase reacted effluent 172. Excess undissolved hydrogen gas andlight ends are vented from the top of the reaction zone(s) through vent173. The quantity of hydrogen gas 168 added to the hydrocarbonaceousreacted effluent 164 is adjusted by valve 169, which is controlled bylevel controller 171. The reacted effluent 172 is then passed throughheat exchanger 175 to lower the temperature of the reacted effluent andto facilitate the separation of light end hydrocarbons, water, otherreaction by-products, and excess hydrogen from the reacted effluent 172into the gas phase to create multi-phase reacted effluent 177comprising: 1) a gas phase reacted effluent and a liquid phasehydrocarbonaceous reacted effluent or 2) a gas phase reacted effluent, aliquid phase hydrocarbonaceous reacted effluent, and liquid water oraqueous phase. The multi-phase reacted effluent 177 is then introducedinto separator 180 and separated into as many as three separatecomponents: liquid water or aqueous phase 182, liquid hydrocarbonaceousreacted effluent 184, and gas phase reacted effluent 186. The rate atwhich the gas phase reacted effluent 186 exits the separator 180 isadjusted by valve 187.

Additional hydrogen gas 188 is then mixed with and dissolved into theliquid hydrocarbonaceous reacted effluent 184 and fed into a finalreactor 190 and reacted in the reactor's reaction zone(s) to form afinal liquid phase reacted effluent 192. Excess undissolved hydrogen gasand light ends may be vented from the top of the reaction zone(s)through vent 193. The quantity of hydrogen gas 188 added to the liquidhydrocarbonaceous reacted effluent 184 is adjusted by valve 189, whichis controlled by level controller 191. The final reacted effluent 192 isthen passed through heat exchanger 195 to lower the temperature of thereacted effluent 192 and to facilitate the separation of light endhydrocarbons, water, other reaction by-products, and excess hydrogenfrom the reacted effluent 192 into the gas phase to create multi-phasereacted effluent 197 comprising: 1) a gas phase reacted effluent and aliquid phase hydrocarbonaceous reacted effluent or 2) a gas phasereacted effluent, a liquid phase hydrocarbonaceous reacted effluent, andliquid water or aqueous phase. The multi-phase reacted effluent 197 isthen introduced into separator 200 and separated into as many as threeseparate components: liquid water or aqueous phase 202, final liquidhydrocarbonaceous product 204, and gas phase reacted effluent 206.

A portion of final hydrocarbonaceous product 204 may then be used toform the diluent stream 103 that is mixed with the initialhigh-contaminant and/or high-olefinic feedstock 101 at the start of theprocess. Although not shown, the final product 204 or other intermediateliquid hydrocarbonaceous product streams may also be recycled and usedas added diluent for any feedstream introduced into any of the initialor intermediate reactors to facilitate dissolution of hydrogen.Alternatively, diluent from another source may be mixed with the initialfeedstock 101 or intermediate feed streams.

FIG. 2 shows a flow diagram schematic of another hydroprocessing systemgenerally designated by the numeral 300. A high-contaminant and/orhigh-olefinic feedstock 301, which may be formed from thosehigh-contaminant and/or high-olefinic feedstocks described herein, suchas a non-petroleum, renewable material, such as pyrolysis oil, thatcontains high levels of oxygen (e.g. greater than 10% by weight) istreated in the system 300. The feedstock 301 is mixed with a liquiddiluent 303 to form a liquid feedstock-diluent mixture 304. Hydrogen gas305 is mixed with and dissolved in the liquid feedstock-diluent mixture304 to form a liquid phase feedstock, diluent, and hydrogen mixture 306.The feedstock, diluent, and hydrogen mixture 306 is then passed throughheat exchanger 308 to increase the temperature of the feedstock,diluent, and hydrogen mixture 306 and then fed into reactor 310,containing a plurality of reaction zones, shown here as 310 a, 310 b,310 c, and 310 d, where the feedstock, diluent, and hydrogen mixture 306is reacted to form reacted effluent 316.

Additional hydrogen gas may be supplied and dissolved in the reactingfeedstock, diluent, and hydrogen mixture 306 in between reaction zonesat hydrogen inputs 312 b, 312 c, and 312 d. The top of each reactionzone 310 a, 310 b, 310 c, and 310 d may be vented by vents 314 a, 314 b,314 c, and 314 d to remove excess undissolved hydrogen gas and lightends. In other embodiments, no such venting may occur. In embodimentswhere the feed has a high oxygen content, water is one of the reactionproducts. Reacted effluent 316, which contains water, is passed throughheat exchanger 318 to lower the temperature of the reacted effluent 316and to facilitate the separation of light end hydrocarbons, water, otherreaction by-products, and excess hydrogen from the reacted effluent 316into the gas phase to create multi-phase reacted effluent 319 comprisinga gas phase reacted effluent, a liquid phase hydrocarbonaceous reactedeffluent, and liquid water or aqueous phase.

The multi-phase reacted effluent 319 is then introduced into separator320 and separated into three components: liquid water or aqueous phase322, gas phase reacted effluent 323, and hydrocarbonaceous reactedeffluent 324. Hydrocarbonaceous reacted effluent 324 is then split intomultiple streams. Optionally, a first portion of hydrocarbonaceousreacted effluent 324 may be utilized as a secondary diluent stream 324a, which can be combined with diluent 303. A second portion ofhydrocarbonaceous reacted effluent 324 can serve as a product stream 324b. A third portion of hydrocarbonaceous reacted effluent 324 is requiredfor the continuation of the process and becomes reacted effluent portion324 c.

Hydrogen gas 325 is then mixed with and dissolved in reacted effluentportion 324 c to form a liquid phase reacted effluent and hydrogenmixture 326. The reacted effluent and hydrogen mixture 326 is thenpassed through heat exchanger 328 to increase the temperature of thereacted effluent and hydrogen mixture 326 and then fed into reactor 330,containing a plurality of reaction zones, shown here as 330 a, 330 b,330 c, and 330 d, where the feedstock, diluent, and hydrogen mixture 326is reacted to form reacted effluent 336.

Additional hydrogen gas is supplied and dissolved in the reactingfeedstock, diluent, and hydrogen mixture 326 in between reaction zonesat hydrogen inputs 332 b, 332 c, and 332 d. The top of each reactionzone 330 a, 330 b, 330 c, and 330 d may be vented by vents 334 a, 334 b,334 c, and 334 d to remove excess undissolved hydrogen gas and lightends. In other embodiments, no such venting occurs. Reacted effluent 336is then passed through heat exchanger 338 to lower the temperature ofthe reacted effluent 336 and to facilitate the separation of light endhydrocarbons, any water, other reaction by-products, and excess hydrogenfrom the reacted effluent 336 into the gas phase to create multi-phasereacted effluent 339 comprising a gas phase reacted effluent, a liquidphase hydrocarbonaceous reacted effluent, and any liquid water oraqueous phase.

The multi-phase reacted effluent 339 is then introduced into separator340 and separated into three components: liquid water or aqueous phase342, gas phase reacted effluent 343, and final hydrocarbonaceous product344. A portion of the hydrocarbonaceous product 344 is used to form thediluent stream 303 that may be mixed with the initial high-contaminantand/or high-olefinic feedstock 301 as the start of the process. Theamount of diluent 303 and/or 324 a added may be that selected todissolve a preselected amount of hydrogen gas in the combinedfeed-diluent mixture; to maintain the temperature within the reactor(s)below a preselected temperature; or to adjust the capacity of the liquidphase to dissolve or carry water; or a combination of these.

FIG. 3 shows another flow diagram schematic for a hydroprocessing systemgenerally designated by the numeral 500. A high-contaminant and/orhigh-olefinic feedstock 501, such as those that have been describedherein, is mixed with a liquid diluent 503 to form a liquidfeedstock-diluent mixture 504. A controlled amount of hydrogen gas 505is then mixed with and dissolved in the liquid feedstock-diluent mixture304 to form a liquid phase feedstock, diluent, and hydrogen mixture 508.

The liquid feedstock, diluent, and hydrogen mixture 508 is thenintroduced into reactor 510 and reacted in the reactor's reactionzone(s) to form a liquid phase reacted effluent 512. Excess undissolvedhydrogen gas and light ends 511 may be vented from the top of thereaction zone(s). In other embodiments, no venting of hydrogen gas fromthe reactor(s) occurs. Reacted effluent 512 then passes into flashvessel 515 where the reacted effluent 512 is split into two streams: agas phase flash vessel effluent 516 and a liquid phase flash vesseleffluent 517. The gas phase flash vessel effluent 516 is passed througha heat exchanger 518 to reduce the temperature of the gas phase flashvessel effluent 516 and to facilitate the condensation of a portion ofthe vapor phase flash vessel effluent 516 from the gas phase to theliquid phase and forming a multi-phase flash vessel effluent 519. Themulti-phase flash vessel effluent is then introduced into a separator520 and separated into three components: liquid water or aqueous phase521, gas phase effluent 522, and liquid hydrocarbonaceous effluent 524.The quantity of gas phase effluent 522 exiting the separator 520 isadjusted by valve 523, which may serve to control the pressure inreactor 510 through pressure controller 514.

The liquid hydrocarbonaceous effluent 524 is then combined with theliquid phase flash vessel effluent 517 before being mixed with acontrolled amount of hydrogen gas 525 to form a liquid phaseintermediate feed 527. Intermediate feed 527 is then introduced intoreactor 530 and reacted in the reactor's reaction zone(s) to form aliquid phase reacted effluent 532. Excess undissolved hydrogen gas andlight ends 531 may be vented from the top of the reaction zone(s). Inother embodiments, no such venting from the reactor occurs. Reactedeffluent 532 then passes into flash vessel 535 where the reactedeffluent 532 is split into two streams: a gas phase flash vesseleffluent 536 and a liquid phase flash vessel effluent 537. The gas phaseflash vessel effluent 536 is passed through a heat exchanger to reducethe temperature of the gas phase flash vessel effluent 536 and tofacilitate the condensation of a portion of the vapor phase flash vesseleffluent 536 from the gas phase to the liquid phase and forming amulti-phase flash vessel effluent 539.

The multi-phase flash vessel effluent is then introduced into aseparator 540 and separated into three components: liquid water oraqueous phase 541, gas phase effluent 542, and liquid hydrocarbonaceouseffluent 544. The quantity of gas phase effluent 542 exiting theseparator 540 is adjusted by valve 543 which is used to control thequantity of additional hydrogen gas 525 added to the liquid phase flashvessel effluent 517 and the liquid hydrocarbonaceous effluent 524 priorto entry into reactor 530.

The liquid hydrocarbonaceous effluent 544 is then combined with theliquid phase flash vessel effluent 537 before being mixed with hydrogengas 545 to form a liquid phase intermediate feed 547. Intermediate feed547 is then introduced into reactor 550 and reacted in the reactor'sreaction zone(s) to form a liquid phase reacted effluent 552. Excessundissolved hydrogen gas and light ends 551 may be vented from the topof the reaction zone(s). In other embodiments, no venting of the reactoroccurs. Reacted effluent 552 then passes into flash vessel 555 where thereacted effluent 552 is split into two streams: a gas phase flash vesseleffluent 556 and a liquid phase flash vessel effluent 557. The gas phaseflash vessel effluent 556 is passed through a heat exchanger to reducethe temperature of the gas phase flash vessel effluent 556 and tofacilitate the condensation of a portion of the vapor phase flash vesseleffluent 556 from the gas phase to the liquid phase and forming amulti-phase flash vessel effluent 559.

The multi-phase flash vessel effluent is then introduced into aseparator 560 and separated into three components: liquid water oraqueous phase 561, gas phase effluent 562, and liquid hydrocarbonaceouseffluent 564. The quantity of gas phase effluent 562 exiting theseparator 560 is adjusted by valve 563, which is used to control thequantity of additional hydrogen gas 545 added to the liquid phase flashvessel effluent 537 and the liquid hydrocarbonaceous effluent 544 priorto entry into reactor 550. The liquid hydrocarbonaceous effluent 564 isthen combined with the liquid phase flash vessel effluent 557 to form afinal product stream 566. A portion of the final product stream 566 maythen be used to form the diluent stream 503 that is mixed withhigh-contaminant and/or high-olefinic feedstock 501 at the start of theprocess. The amount of diluent 503 added may be that sufficient todissolve a preselected amount of hydrogen in the combined feed-diluentmixture; to maintain the temperature within the reactor(s) below apreselected temperature; or to adjust the capacity of the liquid phaseto dissolve or carry water; or a combination of any of these.

FIG. 4 shows an example of a reactor 600 that may be used in any of thesystems described herein. The reactor 600 includes a reactor vessel 602that houses the various internal components of the reactor. The reactor600 is provided with an inlet 604 at the upper end that is fluidlycoupled to a feed line 606. The feed line 606 combines liquid feed 608,which may be a high-contaminant and/or high-olefinic non-petroleumliquid feed to be treated, with diluent or recycle feeds 610 and/or 612.The feed/diluent mixture is passed through line 614 where hydrogen gasis added to the feed/diluent mixture through line 616. The amount ofhydrogen gas added is controlled by control valve 618 that is coupled toa hydrogen gas source.

The feed/diluent/hydrogen mixture is introduced into the reactor inlet604 from feed line 606. The feed mixture is in a liquid phase, which maybe a continuous liquid phase. The inlet 604 is fluidly coupled to adistributor 620. The liquid feed/diluent/hydrogen mixture is passedthrough the distributor 620 to catalyst bed 622 of an upper firstreaction zone 624 containing a hydroprocessing catalyst. Hydrogen gas,which may be excess hydrogen gas, may also be passed through thedistributor 620, and be present within the reactor vessel 602. Thedistributor 620 distributes the liquid feed/diluent/hydrogen over thecatalyst bed 622. The feed mixture from the distributor 620 is passed asa liquid “bubbling feed” that may be in the form of a liquid stream orstreams, which may or may not contain hydrogen gas, that is distributedover the catalyst bed 622 and should be distinguished from aconventional trickle bed reactor processes wherein large amounts ofhydrogen gas are circulated through the catalyst bed.

Reacted liquid 624 is collected in the bottom of the reaction zone 622.The reacted liquid 624 is passed through outlet collector assembly 626having an outlet conduit 628 that is fluidly coupled to a distributor630 of a lower second reaction zone 632. The effluent from reaction zone624 is passed from distributor 630 to second catalyst bed 634, which maycontain the same or a different hydroprocessing catalyst from that ofcatalyst bed 622.

The reacted liquid of reaction zone 632 is collected at the bottom ofthe reactor 600 and is passed to outlet collector 636 to outlet conduit638 and out of the reactor 600. Thi effluent is passed from conduit 638to pump 640. All or a portion of the effluent from pump 640 may bepassed through line 642 for further processing or as product. A portionmay also be used as diluent as recycle 610. The diluents 612 may be aseparate diluent source or a recycle from a different part of the systemin which the reactor 600 is utilized.

While the reactor 600 is shown with two reaction zones, it may be alsobe configured to have a single reaction zone or three or more as well.Furthermore, the reactor 600 may be modified so that liquid collectedfrom the upper reaction zone 624 is removed from the reactor through anoutlet (not shown) and introduced into a separator and/or heat exchanger(not shown) where it may be flashed, cooled, and/or separated intodifferent products (e.g. gases, hydrocarbons, water, etc.). The liquidproduct to be treated may then be reintroduced into the second reactionzone 632 through an inlet (not shown). Where more than two reactionzones exist in the reactor, such removal and reintroduction may occurwith one or more of each of the reaction zones. Hydrogen and additionaldiluents may also be added to the reintroduced liquid between eachreaction zone.

The following examples better serve to illustrate the invention.

EXAMPLES Example 1

A pyrolysis oil derived from waste wood was hydrotreated in a systemhaving two reaction zones, each containing a hydroprocessing catalyst.The pyrolysis oil had a specific gravity of 1.25, a sulfur content of0.35% by weight, a nitrogen content of 0.28% by weight and an oxygencontent of 35% by weight. Hydrogen gas was added to each the feeds priorto introduction into the reaction zones so that sufficient hydrogennecessary for the reaction was dissolved in the feeds introduced as aliquid phase. The reaction products were removed from each zone andcooled to 280° F. after each reaction zone. Water was removed from eachof the cooled reaction products from each reaction zone. Approximately40% of the water was removed after the first reaction zone and 60% wasremoved after the second reaction zone. All of the liquid reactionproduct from the first reaction zone with the water removed was used asthe feed for the second reaction zone. Approximately 85% of the liquidreaction product from the second reaction zone with the water removedwas used as a recycle ahead of the first reaction zone. Approximately60% of the hydrogen was added to the first reaction zone and 40% of thehydrogen was added to the second reaction zone. In both cases thehydrogen addition was at a 10% excess above the solubility limit of thereaction zone feed mixture. The startup diluent used was a hydrocarbonsimilar to the water-free reaction product from the second reactionzone.

The reaction conditions in each reaction zone were as set forth in Table1 below:

TABLE 1 Pressure 1850 psig Reactor Weighted Ave. Bed Temp. (WABT) 650°F. Catalyst Volume LHSV hr⁻¹: 3 Recycle Ratio (weight basis) - Recycleto Feed 5 to 1 Hydrogen Addition to Feed 4200 SCF/BBl feed

The following products, as set forth in Table 2 below, were obtainedfrom the treatment:

TABLE 2 Product Amount Light Ends (H₂S, NH₃, light hydrocarbons)  15 wt.% of feed oil Naptha  35 wt. % of feed oil Diesel  15 wt. % of feed oilHeavy Ends  3 wt. % of feed oil Water  35 wt. % of feed oil Total 103wt. % of feed oil

Example 2

A pyrolysis oil derived from waste wood was hydrotreated in a systemhaving a single reaction zone containing a hydroprocessing catalyst. Thepyrolysis oil had a specific gravity of 1.25, a sulfur content of 0.35%by weight, a nitrogen content of 0.28% by weight and an oxygen contentof 35% by weight. Hydrogen gas was added to the feed prior tointroduction into the reaction zone so that sufficient hydrogennecessary for the reaction was dissolved in the feed introduced as aliquid phase. The reaction products were removed from the reaction zoneand cooled to 280° F. Water at 100% was removed from the cooled reactionproducts. Approximately 95% of the reaction product with the waterremoved was used as a recycle ahead of the reaction zone. All of thehydrogen was added to the reaction zone at a 10% excess above thesolubility limit of the feed mixture. The startup diluent used was ahydrocarbon similar to the water-free reaction product.

The reaction conditions in the reaction zone were as set forth in Table3 below:

TABLE 3 Pressure 2055 psig Reactor Weighted Ave. Bed Temp. (WABT) 660°F. Catalyst Volume LHSV hr⁻¹: 2 Recycle Ratio (weight basis) - Recycleto Feed 11 to 1 Hydrogen Addition to Feed 4700 SCF/BBl feed

The following products, as set forth in Table 4 below, were obtainedfrom the treatment:

TABLE 4 Product Amount Light Ends (H₂S, NH₃, light hydrocarbons)  13 wt.% of feed oil Naptha  37 wt. % of feed oil Diesel  14 wt. % of feed oilHeavy Ends  5 wt. % of feed oil Water  35 wt. % of feed oil Total 104wt. % of feed oil

Example 3

A pyrolysis oil derived from waste wood was hydrotreated in a systemhaving two reaction zones containing a hydroprocessing catalyst. Thepyrolysis oil had a specific gravity of 1.25, a sulfur content of 0.35%by weight, a nitrogen content of 0.28% by weight and an oxygen contentof 35% by weight. Hydrogen gas was added to the feeds prior tointroduction into the reaction zones so that sufficient hydrogennecessary for the reaction was dissolved in the feeds and introduced asa liquid phase. The reaction products were removed from each zone andcooled to 280° F. after each reaction zone. Water was removed from eachof the cooled reaction products from each reaction zone. Approximately40% of the water was removed after the first reaction zone and 60% wasremoved after the second reaction zone. All of the liquid reactionproduct from the first reaction zone with the water removed was used asthe feed for the second reaction zone. Approximately 85% of the liquidreaction product from the second reaction zone with the water removedwas used as a recycle ahead of the first reaction zone. Approximately60% of the hydrogen was added to the first reaction zone and 40% of thehydrogen was added to the second reaction zone. In both cases thehydrogen addition was at a 10% excess above the solubility limit of thefeed mixture. The startup diluent used was a hydrocarbon similar to thewater-free reaction product from the second reaction zone.

The reaction conditions in each reaction zone were as set forth in Table5 below:

TABLE 5 Pressure 1100 psig Reactor Weighted Ave. Bed Temp. (WABT) 680°F. Catalyst Volume LHSV hr⁻¹: 1.5 Recycle Ratio (weight basis) - Recycleto Feed 10 to 1 Hydrogen Addition to Feed 3900 SCF/BBl feed

The following products, as set forth in Table 6 below, were obtainedfrom the treatment:

TABLE 6 Product Amount Light Ends (H₂S, NH₃, light hydrocarbons)  14 wt.% of feed oil Naptha  30 wt. % of feed oil Diesel  16 wt. % of feed oilHeavy Ends  8 wt. % of feed oil Water  35 wt. % of feed oil Total 103wt. % of feed oil

While the invention has been shown in only some of its forms, it shouldbe apparent to those skilled in the art that it is not so limited, butis susceptible to various changes and modifications without departingfrom the scope of the invention. Accordingly, it is appropriate that theappended claims be construed broadly and in a manner consistent with thescope of the invention.

We claim:
 1. A method of hydroprocessing comprising: (a) introducing anon-petroleum feed containing from about 10% or more oxygen by weight tobe treated along with a diluent and hydrogen into a first reaction zonecontaining a hydroprocessing catalyst, the amount of diluent combinedwith the non-petroleum feed being selected to (A) dissolve a preselectedamount of hydrogen in the combined non-petroleum/diluent feed; (B)maintain the temperature within the reactor below a preselectedtemperature; and/or (C) adjust the capacity of the liquid phase todissolve or carry water and hydrogen; (b) allowing the feed and hydrogento react in a liquid phase within the first reaction zone to producereaction products, at least one of the reaction products being water;(c) removing the reaction products from the first reaction zone; (d)separating water from the removed reaction products as an aqueous phaseto provide a separated reaction product that is free from the separatedwater; and (e) introducing at least a portion of the separated reactionproduct as a feed along with hydrogen into a second reaction zonecontaining a hydroprocessing catalyst; and (f) allowing the separatedreaction product feed and hydrogen to react in a liquid phase within thesecond reaction zone to produce a second-reaction-zone reaction product.2. The method of claim 1, wherein: the diluent is provided by at leastone of (1) a further portion of the separated reaction product of step(d) and (2) at least a portion of the second-reaction-zone reactionproduct of step (f).
 3. The method of claim 1, wherein: the separatedreaction product is substantially water-free.
 4. The method of claim 1,wherein: water makes up at least 10% by weight of the total reactionproducts.
 5. The method of claim 1, wherein: water makes up at least 20%by weight of the total reaction products.
 6. The method of claim 1,wherein: water makes up at least 30% by weight of the total reactionproducts.
 7. The method of claim 1, wherein: the non-petroleum feed iscomprised of pyrolysis oils.
 8. The method of claim 7, wherein: thepyrolysis oils are derived from at least one of cellulosic biomassmaterials and coal.
 9. The method of claim 1, wherein: the non-petroleumfeed to be treated is comprised of at least 20% by weight oxygen. 10.The method of claim 1, wherein: the non-petroleum feed is introduced inthe first reaction zone under conditions so that substantially all thefeed and hydrogen are in a continuous liquid phase within the firstreaction zone.
 11. The method of claim 1, wherein: the removed reactionproducts of step (c) are cooled prior to separating water according to(d).
 12. The method of claim 1, wherein: the first and second reactionzones are reactors and wherein each reactor contains greater than 10%hydrogen gas by total volume of the reactor.
 13. The method of claim 1,wherein: no excess hydrogen gas is vented from the first and secondreaction zones to facilitate controlling quantities of liquids withinthe reaction zones.
 14. A method of hydroprocessing comprising: (a)introducing a non-petroleum feed containing from about 10% or moreoxygen by weight to be treated along with a diluent and hydrogen into afirst reaction zone containing a hydroprocessing catalyst, the amount ofdiluent combined with the non-petroleum feed being selected to (A)dissolve a preselected amount of hydrogen in the combinednon-petroleum/diluent feed; (B) maintain the temperature within thereactor below a preselected temperature; and/or (C) adjust the capacityof the liquid phase to dissolve or carry water; (b) allowing the feedand hydrogen to react in a liquid phase within the first reaction zoneto produce reaction products, at least one of the reaction productsbeing water; (c) removing the reaction products from the first reactionzone; (d) cooling the removed reaction products; (e) separating waterfrom the removed reaction products to provide a separated reactionproduct that is free from the separated water; (f) introducing at leasta portion of the separated reaction product as a feed along withhydrogen into a second reaction zone containing a hydroprocessingcatalyst; (g) allowing the separated reaction products and hydrogen toreact in a liquid phase within the second reaction zone to producereaction products; (h) removing the reaction products produced in (g)from the second reaction zone; (i) cooling the removed reaction productsfrom (h); and (j) separating any gas phase and any liquid water phasefrom the cooled reaction products from (i) to form a separated reactionproduct that is free from any separated liquid water to provided aseparated liquid reaction product.
 15. The method of claim 14, wherein:the diluent is provided by at least one of (1) a further portion of theseparated reaction product of step (e) and (2) at least a portion of theseparated liquid reaction product of step (j).
 16. The method of claim14, wherein: the separated reaction products of steps (e) and (j) aresubstantially water-free.
 17. The method of claim 14, wherein: watermakes up at least 10% by weight of the total reaction products.
 18. Themethod of claim 14, wherein: water makes up at least 20% by weight ofthe total reaction products.
 19. The method of claim 14, wherein: watermakes up at least 30% by weight of the total reaction products.
 20. Amethod of hydroprocessing comprising: (a) introducing a non-petroleumfeed to be treated containing from about 10% or more by total weight offeed of at least one of olefinic compounds and heteroatom contaminantsalong with a diluent and hydrogen into a first reaction zone containinga hydroprocessing catalyst, the amount of diluent combined with thenon-petroleum feed being selected to (A) dissolve a preselected amountof hydrogen in the combined non-petroleum/diluent feed; (B) maintain thetemperature within the reactor below a preselected temperature; and/or(C) adjust the capacity of the liquid phase to dissolve or carry water;(b) allowing the feed and hydrogen to react in a liquid phase within thefirst reaction zone to produce reaction products; (c) removing thereaction products from the first reaction zone; (d) cooling the removedreaction product; (e) introducing at least a portion of the cooledreaction product as a feed along with hydrogen into a second reactionzone containing a hydroprocessing catalyst; and (f) allowing the cooledreaction product and hydrogen to react in a liquid phase within thesecond reaction zone to produce a second-reaction-zone reaction product.